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81.
A. I. Ermakov A. E. Merkulov A. A. Svechnikova V. V. Belousov 《Journal of Structural Chemistry》2004,45(6):923-928
Orbital relaxation (OR) amounts to variation of the orbital exponents in hydrogen molecules and ions relative to the exponents of the isolated atom; it is represented as the sum of the one- and two-center contributions depending on the effective atomic charge and on the presence of other atoms in the molecule. The procedure for isolating the contributions of the exponent includes treatment of the OR of hydrogen in a special set of neutral and charged atoms and molecules with certain multiplicities of their electronic states. Within the framework of the spin-unrestricted Hartree-Fock method, we found and discussed the optimal values of the exponents of the basis orbitals of hydrogen atoms and molecules using the minimal split valence-shell basis set, the basis set that includes the polarization function, and the expanded set of grouped natural orbitals. A simple energy model is suggested for OR. Expressions are derived for evaluating the exponents of the relaxed orbitals in hydrogen-containing systems.Original Russian Text Copyright © 2004 by A. I. Ermakov, A. E. Merkulov, A. A. Svechnikova, and V. V. Belousov__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 6, pp. 973–978, November–December, 2004. 相似文献
82.
A mathematical framework for translational Brownian motion on hypersurfaces is presented, using an imbedding of the surface and Ito diffusions in the ambient space. This includes a survey of Ito calculus and differential geometry. Computational methods for time correlation functions relevant to spin relaxation studies on curved interfaces are given, and explicit calculations of time correlation functions and order parameters for a Rippled surface are presented. 相似文献
83.
Quantum equations of motion describing the energy transfer dynamics via intramolecular anharmonic coupling are presented and solved numerically. Dynamical features of the average excitations of a homogeneous system (SF6) and a heterogeneous system (H/W) are quantitatively discussed in terms of the intramolecular vibrational relaxation (IVR) rates. Possible mechanisms of surface-enhanced desorption via low-power laser radiation are proposed.This work was supported in part by the Office of Naval Research, the Air Force Office of Scientific Research (AFSC), United States Air Force, under Grant AFOSR-82-0046 and the National Science Foundation under Grant No. CHE-8022874Camille and Henry Dreyfus Teacher-Scholar (1975–82) 相似文献
84.
Hirofumi Ono Hiroyuki Yamada Shigenobu Matsuda Kunihiko Okajima Takeshi Kawamoto Hideki Iijima 《Cellulose (London, England)》1998,5(4):231-247
An intensive study for aqueous microcrystalline cellulose (MCC) suspensions was carried out in view of the relationship between a viscosity and a 1H spin-spin relaxation time (T2) of water. An investigation was carried out for four suspension systems with the different particle size distributions. The proton mole ratio () of bound water against MCC particles and T2 of bound water (T2,b) were evaluated from the T2 values obtained by Carr-Purcell- Meiboom-Gill (C.P.M.G) method and those by solid echo method, respectively. As a result of these analyses, the T2,b value for the aqueous MCC suspension was evaluated as 5 × 10–3 s and it was found that the system having a larger tended to show a higher viscosity. By relating the above results to the observation of the suspensions by an optical microscope, it was concluded that a network formed by MCC particles plays an important role in generating a high viscosity of MCC suspension, and that an averaged mobility of water molecules is sensitively affected by the network structure. 相似文献
85.
Minimizing molecular mobility for desiccation preservation of biologics close to ambient temperature using trehalose glasses require quantitative characterization of their enthalpic relaxation at various end water contents. Differential scanning calorimetry (DSC) was used to characterize three different water contents: 0%, 1.5% and 10% over a wide range of aging temperatures. Results showed the characteristic time (τ) varies both with the water content and the aging temperature. τ increased with lowered aging temperature but showed a non-monotonous relationship as a function of water content. Fragility of trehalose glasses was analyzed using thermophysical parameters obtained from relaxation studies. The study showed trehalose to be a fragile glass former at all water contents, with 0% water samples showing a relatively stronger glass. A compromise between molecular mobility and glass fragility led to an optimal water content close to 1.5% and an aging temperature close to room temperature. This would ensure a τ value of 9000 h, which corresponds to a storage period of a year. 相似文献
86.
W. Ren 《Colloid and polymer science》1992,270(10):990-998
Inverse relaxation is studied for hard elastic polypropylene (HEPP), rubber and non-elastic polypropylene. The results show that contractive stress, stress, and internal friction are three essential factors related to the phenomenon. A three-element model in which each element has a definite meaning is proposed to describe this phenomenon. The results also show that, in the first cyclic deformation, relaxation time increases with the increase of recovery for all the materials, which indicates that recovery viscosity increases with the increase of recovery, but the stress rising amplitude (SRA) of inverse relaxation has a maximum in the recovery range. Analysis indicates that SRA equals recovery internal friction (RIF) for ideal material in which stress is solely a function of strain, independent of paths, and approximately equals RIF for non-ideal material at a given strain. From this principle it is found that the order of the work counteracted by RIF for the four materials is the same as that of their second hysteresis loop, and the RIF of HEPP has a sudden increase at the later recovery range. 相似文献
87.
Proton relaxation time measurements are performed for 6m aqueous solutions of7LiI and6LiI in D2O containing small amounts of H2O. The measurements are done at low temperatures and yield maxima of the relaxation rate plotted against 1/T. From the maxima of the relaxation rates, proteon-I– and proton-Li+ distances in the first coordination sphere of the ions are determined, and from the knowledge of the ion-water oxygen distance it is shown that for iodide a somewhat broadened H-bonded configuration is valid and that for Li+ the electric dipole orientation deviates from the radial direction. In order to test the reliability of the method a proton-127I interaction study is also performed in KI solution in glycerol. The I-H distance obtained is in satisfactory agreement with that found in the aqueous system. 相似文献
88.
Hideki Takayasu Misako Takayasu Astero Provata Greg Huber 《Journal of statistical physics》1991,65(3-4):725-745
We study a generalized aggregation process in which charged particles diffuse and coalesce randomly on a lattice. For one-dimensional and mean-field models, we show that there exists a statistically-invariant steady state when randomly charged particles are continuously injected. The steady-state charge distribution obeys a power law with the exponent depending both on the type of the injection and on the spatial dimension. The response of the system to a perturbation (i.e., relaxation) is characterized by either a power law decay (t
–
,1) or a compressed exponential decay [exp(–t
),>1]. 相似文献
89.
H.?J.?M.?BouwmeesterEmail author M.?W.?Den?Otter B.?A.?Boukamp 《Journal of Solid State Electrochemistry》2004,8(9):599-605
The surface exchange coefficient and chemical diffusion coefficient of oxygen for the perovskites La0.6Sr0.4Co1–yFeyO3– (y=0.2, 0.5 and 0.8) were measured using the conductivity relaxation technique. Measurements were performed between 600 and 800 °C in an oxygen partial pressure range between 10–4 and 1 bar. Both transport coefficients decrease markedly with decreasing oxygen partial pressure below about 10–2 bar at all temperatures. This is attributed to ordering of oxygen vacancies. Implications for using La0.6Sr0.4Co1–yFeyO3– as an oxygen separation membrane are discussed.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10-12 April 2003 相似文献
90.
We study the characteristics of phase transition to take the top-priority of randomization in the rules of NaSch model (i.e.noise-first model) into account via computing the relaxation time and the order parameter.The scaling exponents of the relaxation time and the scaling relation of order parameter,respectively,axe obtained. 相似文献